Cyclic (alkyl)(amino)carbenes cAACcy (1b) and cAACmenthyl (1c) react with [Ni(CO)4] to give the 18 VE complexes [Ni(CO)3(cAACcy)] (2b) and [Ni(CO)3(cAACmenthyl)] (2c). With these in hand, the donor-strength and the steric profile of the respective cAAC ligands were evaluated. CAACcy and cAACmenthyl possess similar overall-donating properties (Tolman electronic parameter (TEP) = 2046 (1b) and 2042 (1c)) as common NHCs, though they are also known to be better π-acceptors. 3,3-Diamino-2-aryloxyacrylimidamide 3b, arising from the reaction of cAACcy (1b) with released CO molecules, was obtained as side-product of CO substitution reactions at nickel carbonyls. In contrast to cAACmenthyl (%Vbur = 42), the sterically less encumbered cAACcy (%Vbur = 38) undergoes a subsequent CO substitution at [Ni(CO)3(cAACCy)] (2b) to afford the 16 VE complex [Ni(CO)(cAACcy)2] (4b). Treatment of both [Ni(CO)3(cAACmethyl)] (2a) and [Ni(CO)(cAACmethyl)2] (4a) with allyl bromides led to the formation of cAAC-stabilized allyl nickel...